Resveratrol-based flame retardant materials

ABSTRACT

A process of forming a resveratrol-based flame retardant small molecule with a phosphonate/phosphinate molecule that includes a chloride group and a terminal functional group.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional application of U.S. patent applicationSer. No. 15/609,218, filed May 31, 2017.

BACKGROUND

Plastics are typically derived from a finite and dwindling supply ofpetrochemicals, resulting in price fluctuations and supply chaininstability. Replacing non-renewable petroleum-based polymers withpolymers derived from renewable resources may be desirable. However,there may be limited alternatives to petroleum-based polymers in certaincontexts. To illustrate, particular plastics performance standards maybe specified by a standards body or by a regulatory agency. In somecases, alternatives to petroleum-based polymers may be limited as aresult of challenges associated with satisfying particular plasticsperformance standards.

SUMMARY

According to an embodiment, a process of forming a resveratrol-basedflame retardant small molecule is disclosed. The process includeschemically reacting a resveratrol molecule with a phosphonate moleculethat includes a chloride group and a terminal functional group.

According to another embodiment, a resveratrol-based flame retardantsmall molecule is disclosed having the following formula:

In the above formula, X includes a terminal functional group selectedfrom the group consisting of: an allyl group; an epoxide group; alactone group; an amine group; and a carboxyl group.

According to another embodiment, a process of forming aresveratrol-based flame retardant small molecule is disclosed. Theprocess includes chemically reacting a resveratrol molecule with aphosphinate molecule that includes a chloride group and a terminalfunctional group.

According to yet another embodiment, a resveratrol-based flame retardantsmall molecule is disclosed having the following formula:

In the above formula, X includes a terminal reactive group selected fromthe group consisting of: an allyl group; an epoxide group; a lactonegroup; an amine group; and a carboxyl group.

The foregoing and other objects, features, and advantages of theinvention will be apparent from the following more particulardescriptions of exemplary embodiments of the invention as illustrated inthe accompanying drawings wherein like reference numbers generallyrepresent like parts of exemplary embodiments of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a chemical reaction diagram illustrating a process of forminga first resveratrol-based flame retardant small molecule, according toone embodiment.

FIGS. 2A and 2B are chemical reaction diagrams showing alternativeembodiments of processes of forming a first phosphonate molecule forforming the first resveratrol-based flame retardant small moleculedepicted in FIG. 1.

FIG. 3 is a chemical reaction diagram illustrating a process of forminga second resveratrol-based flame retardant small molecule, according toone embodiment.

FIGS. 4A and 4B are chemical reaction diagrams showing alternativeembodiments of processes of forming a second phosphonate molecule forforming the second resveratrol-based flame retardant small moleculedepicted in FIG. 3.

FIG. 5 is a chemical reaction diagram illustrating a process of forminga third resveratrol-based flame retardant small molecule, according toone embodiment.

FIGS. 6A and 6B are chemical reaction diagrams showing alternativeembodiments of processes of forming a third phosphonate molecule forforming the third resveratrol-based flame retardant small moleculedepicted in FIG. 5.

FIG. 7 is a chemical reaction diagram illustrating a process of forminga fourth resveratrol-based flame retardant small molecule, according toone embodiment.

FIGS. 8A and 8B are chemical reaction diagrams showing alternativeembodiments of processes of forming a fourth phosphonate molecule forforming the fourth resveratrol-based flame retardant small moleculedepicted in FIG. 7.

FIG. 9 is a chemical reaction diagram illustrating a process of forminga fifth resveratrol-based flame retardant small molecule, according toone embodiment.

FIGS. 10A and 10B are chemical reaction diagrams showing alternativeembodiments of processes of forming a fifth phosphonate molecule forforming the fifth resveratrol-based flame retardant small moleculedepicted in FIG. 9.

FIG. 11 is a diagram illustrating an example of a resveratrol-basedflame retardant polymer formed from one of the resveratrol-based flameretardant small molecules depicted in FIGS. 1, 3, 5, 7, and 9.

FIG. 12 is a chemical reaction diagram illustrating a process of forminga sixth resveratrol-based flame retardant small molecule, according toone embodiment.

FIGS. 13A and 13B are chemical reaction diagrams showing alternativeembodiments of processes of forming a first phosphinate molecule forforming for forming the sixth resveratrol-based flame retardant smallmolecule depicted in FIG. 11.

FIG. 14 is a chemical reaction diagram illustrating a process of forminga seventh resveratrol-based flame retardant small molecule, according toone embodiment.

FIGS. 15A and 15B are chemical reaction diagrams showing alternativeembodiments of processes of forming a second phosphinate molecule forforming the seventh resveratrol-based flame retardant small moleculedepicted in FIG. 14.

FIG. 16 is a chemical reaction diagram illustrating a process of formingan eighth resveratrol-based flame retardant small molecule, according toone embodiment.

FIGS. 17A and 17B are chemical reaction diagrams showing alternativeembodiments of processes of forming a third phosphinate molecule forforming the eighth resveratrol-based flame retardant small moleculedepicted in FIG. 16.

FIG. 18 is a chemical reaction diagram illustrating a process of forminga ninth resveratrol-based flame retardant small molecule, according toone embodiment.

FIGS. 19A and 19B are chemical reaction diagrams showing alternativeembodiments of processes of forming a fourth phosphinate molecule forforming the ninth resveratrol-based flame retardant small moleculedepicted in FIG. 18.

FIG. 20 is a chemical reaction diagram illustrating a process of forminga tenth resveratrol-based flame retardant small molecule, according toone embodiment.

FIGS. 21A and 21B are chemical reaction diagrams showing alternativeembodiments of processes of forming a fifth phosphinate molecule forforming the tenth resveratrol-based flame retardant small moleculedepicted in FIG. 20.

FIG. 22 is a diagram illustrating an example of a resveratrol-basedflame retardant polymer formed from one of the resveratrol-based flameretardant small molecules depicted in FIGS. 12, 14, 16, 18, and 20.

DETAILED DESCRIPTION

The present disclosure describes flame retardant materials derived fromthe biorenewable molecule resveratrol (3,5,4′-trihydroxy-trans-stilbene)and methods of forming the flame retardant materials from thebiorenewable molecule resveratrol. The biorenewable molecule resveratrolmay be extracted from plants, where it is produced in response to injuryor when the plant is under attack by pathogens such as bacteria orfungi.

In some embodiments of the present disclosure, a resveratrol moleculemay be chemically reacted with a phosphorus-containing molecule to forma resveratrol-based molecule having one or more phosphorus-based flameretardant moieties. In the present disclosure, the phosphorus-containingmolecule includes a phosphoryl group (i.e., a phosphorus-oxygen doublebond), a chloride group, and an additional reactive functional group(e.g., an allyl group, an epoxide group, a lactone group, an aminegroup, or a carboxyl group). The resveratrol-based molecule having thephosphorus-based flame retardant moiety (or moieties) is also referredto herein as a resveratrol-based flame retardant small molecule. In somecases, the resveratrol-based flame retardant small molecules of thepresent disclosure may be added to a variety of polymeric materials tonot only impart flame retardancy characteristics to the polymericmaterials but also increase the biorenewable content of the polymericmaterials.

In some embodiments of the present disclosure, the additional reactivefunctional group may enable the resveratrol-based flame retardant smallmolecule to be utilized as a monomer to form a resveratrol-based polymerhaving phosphorus-based flame retardant moieties. The resveratrol-basedpolymers having the phosphorus-based flame retardant moieties are alsoreferred to herein as resveratrol-based flame retardant polymers. Insome cases, the resveratrol-based flame retardant polymers of thepresent disclosure may be utilized as stand-alone polymers. In othercases, the resveratrol-based flame retardant polymers of the presentdisclosure may be blended with other polymeric materials (e.g.,petroleum-based polymers) to form a polymeric blend. In such cases, theresveratrol-based flame retardant polymers not only impart flameretardancy characteristics to the polymeric blend but also increase thebiorenewable content of the polymeric blend.

Referring to FIG. 1, a chemical reaction diagram 100 illustrates aprocess of forming a first resveratrol-based flame retardant (FR) smallmolecule 102, according to one embodiment. In the particular embodimentdepicted in FIG. 1, the first resveratrol-based FR small molecule 102 isformed via a chemical reaction of a resveratrol molecule 104 (which maybe derived from plants) and a first phosphonate molecule 106. As furtherdescribed herein, the first phosphonate molecule 106 depicted in FIG. 1may be synthesized according to one of the processes described hereinwith respect to FIGS. 2A and 2B.

The first phosphonate molecule 106 depicted in FIG. 1 represents anexample of a phosphorus-containing molecule in which the additionalreactive group corresponds to an allyl group. FIG. 1 illustrates that achloride group of the first phosphonate molecule 106 reacts with ahydroxyl group of the resveratrol molecule 104 to form aphosphorus-oxygen single bond between the phosphorus atom of thephosphoryl group and the oxygen atom of the hydroxyl group. As aprophetic example, the resveratrol molecule 104 may be chemicallyreacted with the first phosphonate molecule 106 in an amine solvent toyield the first resveratrol-based FR small molecule 102.

In the embodiment depicted in FIG. 1, each hydroxyl group of the threehydroxyl groups of the resveratrol molecule 104 chemically reacts withthe chloride group of the first phosphonate molecule 106 to form thefirst resveratrol-based FR small molecule 102 having threephosphorus-based flame retardant moieties (and three allyl functionalgroups). It will be appreciated that, in other cases, the reactionstoichiometry may be adjusted to form an alternative resveratrol-basedFR small molecule having less than three phosphorus-based flameretardant moieties (and less than three allyl functional groups).

Thus, FIG. 1 illustrates an example of a process of forming aresveratrol-based flame retardant small molecule that includes an allylfunctional group via a chemical reaction of a resveratrol molecule and aphosphonate molecule that includes the allyl functional group.

FIGS. 2A and 2B are chemical reaction diagrams showing alternativeembodiments of processes of forming the first phosphonate molecule 106depicted in FIG. 1. The first phosphonate molecule 106 depicted in FIGS.2A and 2B represents an example of a phosphonate molecule that isfunctionalized with a chloride group for bonding with a hydroxyl groupof a resveratrol molecule and an allyl functional group that may beutilized to form a resveratrol-derived flame retardant polymer, asdescribed further herein with respect to FIG. 11.

Referring to FIG. 2A, a first chemical reaction diagram 200 illustratesa first embodiment of a process of forming the first phosphonatemolecule 106. In FIG. 2A, the first phosphonate molecule 106 is formedvia a one-step process via reaction of allyl alcohol with phenyldichlorophosphate via careful addition and stoichiometric control.

As a prophetic example, to a stirred solution that includes allylalcohol (1.0 eq.) and triethylamine (2.0 eq.) in anhydrous THF, phenyldichlorophosphate (1.3 eq.) may be added dropwise at 0° C., and thereaction mixture may be stirred at ambient temperature for 2 hours orthe reaction mixture may be heated up to reflux (60-65° C.) for anextended reaction time (4 hours). The reaction mixture may be cooled toambient temperature and filtered to remove the triethylaminehydrochloride salt. The solvents of the filtrate may be removed invacuo, and the product may be purified by fractional distillation.

Referring to FIG. 2B, a second chemical reaction diagram 210 illustratesan alternative embodiment of a process of forming the first phosphonatemolecule 106. The first chemical reaction depicted in FIG. 2Billustrates that allyl alcohol may be reacted with titanium (IV)isopropoxide and phosphonic acid diphenyl ester via apseudo-esterification to form an intermediate molecule. The secondchemical reaction depicted in FIG. 2B illustrates that the intermediatemolecule may be reacted with thionyl chloride to form the firstphosphonate molecule 106.

As a prophetic example, diaryl phosphite (5.5 mmol) may be added to asolution of titanium (IV) isopropoxide, Ti(OPr)₄ (11 mmol), in allylalcohol (excess). This solution may be diluted with benzene. Thereaction mixture may be heated to 40° C. until completion. The mixturemay be poured into water, extracted with CH₂Cl₂ (3×), dried over MgSO₄,and solvent and volatile components may be removed in vacuo. Theproducts may be purified by fractional distillation orrecrystallization. The product from the first step (1.0 eq.), in dryacetonitrile (MeCN), toluene, or dichloromethane (DCM), may be added toa solution of trichloroisocyanuric acid (0.33 eq.), N-chlorosuccinimide(1.0 eq.), or tert-butyl hypochlorite (1.0 eq.) in the same solvent atroom temperature, under an N₂ atmosphere. Upon formation of aprecipitate, the reaction may be stirred at room temperature for anadditional 2 hours. Upon completion of the reaction, as determined by³¹P NMR, the reaction mixture may be passed through a 0.45 μm Whatmansyringe filter and concentrated under vacuum. Next, thionyl chloride(SOCl₂) may be dissolved in a suitable solvent, such as carbontetrachloride (CCl₄), and the chemical reaction may be performed from 0°C. to room temperature.

Thus, FIGS. 2A and 2B illustrate alternative processes of forming aphosphonate molecule that is functionalized with a chloride group forbonding with a hydroxyl group of a resveratrol molecule and an allylfunctional group that may be utilized to form a resveratrol-based flameretardant polymer. While FIGS. 2A and 2B illustrate an example in whichthe phosphonate molecule includes a phenyl group, it will be appreciatedthat the phenyl group may be substituted by ethyl, methyl, propyl, orisopropyl groups, among other alternatives.

Referring to FIG. 3, a chemical reaction diagram 300 illustrates aprocess of forming a second resveratrol-based FR small molecule 302,according to one embodiment. In the particular embodiment depicted inFIG. 3, the second resveratrol-based FR small molecule 302 is formed viaa chemical reaction of the resveratrol molecule 104 and a secondphosphonate molecule 306. As further described herein, the secondphosphonate molecule 306 depicted in FIG. 3 may be synthesized accordingto one of the processes described herein with respect to FIGS. 4A and4B.

The second phosphonate molecule 306 depicted in FIG. 3 represents anexample of a phosphorus-containing molecule in which the additionalreactive group corresponds to an epoxide group. FIG. 3 illustrates thata chloride group of the second phosphonate molecule 306 reacts with ahydroxyl group of the resveratrol molecule 104 to form aphosphorus-oxygen single bond between the phosphorus atom of thephosphoryl group and the oxygen atom of the hydroxyl group. As aprophetic example, the resveratrol molecule 104 may be chemicallyreacted with the second phosphonate molecule 306 in an amine solvent toyield the second resveratrol-based FR small molecule 302.

In the embodiment depicted in FIG. 3, each hydroxyl group of the threehydroxyl groups of the resveratrol molecule 104 chemically reacts withthe chloride group of the second phosphonate molecule 306 to form thesecond resveratrol-based FR small molecule 302 having threephosphorus-based flame retardant moieties (and three epoxide functionalgroups). It will be appreciated that, in other cases, the reactionstoichiometry may be adjusted to form an alternative resveratrol-basedFR small molecule having less than three phosphorus-based flameretardant moieties (and less than three epoxide functional groups).

Thus, FIG. 3 illustrates an example of a process of forming aresveratrol-derived flame retardant small molecule that includes anepoxide functional group via a chemical reaction of a resveratrolmolecule and a phosphonate molecule that includes the epoxide functionalgroup.

FIGS. 4A and 4B are chemical reaction diagrams showing alternativeembodiments of processes of forming the second phosphonate molecule 306depicted in FIG. 3. The second phosphonate molecule 306 depicted inFIGS. 4A and 4B represents an example of a phosphonate molecule that isfunctionalized with a chloride group for bonding with a hydroxyl groupof a resveratrol molecule and an epoxide functional group that may beutilized to form a resveratrol-based flame retardant polymer, asdescribed further herein with respect to FIG. 11.

Referring to FIG. 4A, a first chemical reaction diagram 400 illustratesa first embodiment of a process of forming the second phosphonatemolecule 306. In FIG. 4A, the second phosphonate molecule 306 is formedvia a one-step process via reaction of glycidol with phenyldichlorophosphate via careful addition and stoichiometric control.

As a prophetic example, to a stirred solution that includes glycidol(1.0 eq.) and triethylamine (2.0 eq.) in anhydrous THF, phenyldichlorophosphate (1.3 eq.) may be added dropwise at 0° C., and thereaction mixture may be stirred at ambient temperature for 2 hours orthe reaction mixture may be heated up to reflux (60-65° C.) for anextended reaction time (4 hours). The reaction mixture may be cooled toambient temperature and filtered to remove the triethylaminehydrochloride salt. The solvents of the filtrate may be removed invacuo, and the product may be purified by fractional distillation.

Referring to FIG. 4B, a second chemical reaction diagram 410 illustratesan alternative embodiment of a process of forming the second phosphonatemolecule 306. The first chemical reaction depicted in FIG. 4Billustrates that glycidol may be reacted with titanium (IV) isopropoxideand phosphonic acid diphenyl ester via a pseudo-esterification to forman intermediate molecule. The second chemical reaction depicted in FIG.4B illustrates that the intermediate molecule may be reacted withthionyl chloride to form the second phosphonate molecule 306.

As a prophetic example, diaryl phosphite (5.5 mmol) may be added to asolution of titanium (IV) isopropoxide, Ti(OPr)₄ (11 mmol), in glycidol(excess). This solution may be diluted with benzene. The reactionmixture may be heated to 40° C. until completion. The mixture may bepoured into water, extracted with CH₂Cl₂ (3×), dried over MgSO₄, andsolvent and volatile components may be removed in vacuo. The productsmay be purified by fractional distillation or recrystallization. Theproduct from the first step (1.0 eq.), in dry acetonitrile (MeCN),toluene, or dichloromethane (DCM), may be added to a solution oftrichloroisocyanuric acid (0.33 eq.), N-chlorosuccinimide (1.0 eq.), ortert-butyl hypochlorite (1.0 eq.) in the same solvent at roomtemperature, under an N₂ atmosphere. Upon formation of a precipitate,the reaction may be stirred at room temperature for an additional 2hours. Upon completion of the reaction, as determined by ³¹P NMR, thereaction mixture may be passed through a 0.45 μm Whatman syringe filterand concentrated under vacuum. Next, thionyl chloride (SOCl₂) may bedissolved in a suitable solvent, such as carbon tetrachloride (CCl₄),and the chemical reaction may be performed from 0° C. to roomtemperature.

Thus, FIGS. 4A and 4B illustrate alternative processes of forming aphosphonate molecule that is functionalized with a chloride group forbonding with a hydroxyl group of a resveratrol molecule and an epoxidefunctional group that may be utilized to form a resveratrol-based flameretardant polymer. While FIGS. 4A and 4B illustrate an example in whichthe phosphonate molecule includes a phenyl group, it will be appreciatedthat the phenyl group may be substituted by ethyl, methyl, propyl, orisopropyl groups, among other alternatives.

Referring to FIG. 5, a chemical reaction diagram 500 illustrates aprocess of forming a third resveratrol-based FR small molecule 502,according to one embodiment. In the particular embodiment depicted inFIG. 5, the third resveratrol-based FR small molecule 502 is formed viaa chemical reaction of the resveratrol molecule 104 and a thirdphosphonate molecule 506. As further described herein, the thirdphosphonate molecule 506 depicted in FIG. 5 may be synthesized accordingto one of the processes described herein with respect to FIGS. 6A and6B.

The third phosphonate molecule 506 depicted in FIG. 5 represents anexample of a phosphorus-containing molecule in which the additionalreactive group corresponds to a lactone group. FIG. 5 illustrates that achloride group of the third phosphonate molecule 506 reacts with ahydroxyl group of the resveratrol molecule 104 to form aphosphorus-oxygen single bond between the phosphorus atom of thephosphoryl group and the oxygen atom of the hydroxyl group. As aprophetic example, the resveratrol molecule 104 may be chemicallyreacted with the third phosphonate molecule 506 in an amine solvent toyield the third resveratrol-based FR small molecule 502.

In the embodiment depicted in FIG. 5, each hydroxyl group of the threehydroxyl groups of the resveratrol molecule 104 chemically reacts withthe chloride group of the third phosphonate molecule 506 to form thethird resveratrol-based FR small molecule 502 having threephosphorus-based flame retardant moieties (and three lactone functionalgroups). It will be appreciated that, in other cases, the reactionstoichiometry may be adjusted to form an alternative resveratrol-basedFR small molecule having less than three phosphorus-based flameretardant moieties (and less than three lactone functional groups).

Thus, FIG. 5 illustrates an example of a process of forming aresveratrol-based flame retardant small molecule that includes a lactonefunctional group via a chemical reaction of a resveratrol molecule and aphosphonate molecule that includes the lactone functional group.

FIGS. 6A and 6B are chemical reaction diagrams showing alternativeembodiments of processes of forming the third phosphonate molecule 506depicted in FIG. 5. The third phosphonate molecule 506 depicted in FIGS.6A and 6B represents an example of a phosphonate molecule that isfunctionalized with a chloride group for bonding with a hydroxyl groupof a resveratrol molecule and a lactone functional group that may beutilized to form a resveratrol-based flame retardant polymer, asdescribed further herein with respect to FIG. 11.

Referring to FIG. 6A, a first chemical reaction diagram 600 illustratesa first embodiment of a process of forming the third phosphonatemolecule 506. In FIG. 6A, the third phosphonate molecule 506 is formedvia a one-step process via reaction of4-Hydroxymethyl-1,3-dioxolan-2-one with phenyl dichlorophosphate viacareful addition and stoichiometric control.

As a prophetic example, to a stirred solution that includes4-Hydroxymethyl-1,3-dioxolan-2-one (1.0 eq.) and triethylamine (2.0 eq.)in anhydrous THF, phenyl dichlorophosphate (1.3 eq.) may be addeddropwise at 0° C., and the reaction mixture may be stirred at ambienttemperature for 2 hours or the reaction mixture may be heated up toreflux (60-65° C.) for an extended reaction time (4 hours). The reactionmixture may be cooled to ambient temperature and filtered to remove thetriethylamine hydrochloride salt. The solvents of the filtrate may beremoved in vacuo, and the product may be purified by fractionaldistillation.

Referring to FIG. 6B, a second chemical reaction diagram 610 illustratesan alternative embodiment of a process of forming the third phosphonatemolecule 506. The first chemical reaction depicted in FIG. 6Billustrates that 4-Hydroxymethyl-1,3-dioxolan-2-one may be reacted withtitanium (IV) isopropoxide and phosphonic acid diphenyl ester via apseudo-esterification to form an intermediate molecule. The secondchemical reaction depicted in FIG. 6B illustrates that the intermediatemolecule may be reacted with thionyl chloride to form the thirdphosphonate molecule 506.

As a prophetic example, diaryl phosphite (5.5 mmol) may be added to asolution of titanium (IV) isopropoxide, Ti(OPr)₄ (11 mmol), in4-Hydroxymethyl-1,3-dioxolan-2-one (excess). This solution may bediluted with benzene. The reaction mixture may be heated to 40° C. untilcompletion. The mixture may be poured into water, extracted with CH₂Cl₂(3×), dried over MgSO₄, and solvent and volatile components may beremoved in vacuo. The products may be purified by fractionaldistillation or recrystallization. The product from the first step (1.0eq.), in dry acetonitrile (MeCN), toluene, or dichloromethane (DCM), maybe added to a solution of trichloroisocyanuric acid (0.33 eq.),N-chlorosuccinimide (1.0 eq.), or tert-butyl hypochlorite (1.0 eq.) inthe same solvent at room temperature, under an N₂ atmosphere. Uponformation of a precipitate, the reaction may be stirred at roomtemperature for an additional 2 hours. Upon completion of the reaction,as determined by ³¹P NMR, the reaction mixture may be passed through a0.45 μm Whatman syringe filter and concentrated under vacuum. Next,thionyl chloride (SOCl₂) may be dissolved in a suitable solvent, such ascarbon tetrachloride (CCl₄), and the chemical reaction may be performedfrom 0° C. to room temperature.

Thus, FIGS. 6A and 6B illustrate alternative processes of forming aphosphonate molecule that is functionalized with a chloride group forbonding with a hydroxyl group of a resveratrol molecule and a lactonefunctional group that may be utilized to form a resveratrol-based flameretardant polymer. While FIGS. 6A and 6B illustrate an example in whichthe phosphonate molecule includes a phenyl group, it will be appreciatedthat the phenyl group may be substituted by ethyl, methyl, propyl, orisopropyl groups, among other alternatives.

Referring to FIG. 7, a chemical reaction diagram 700 illustrates aprocess of forming a fourth resveratrol-based FR small molecule 702,according to one embodiment. In the particular embodiment depicted inFIG. 7, the fourth resveratrol-based FR small molecule 702 is formed viaa chemical reaction of the resveratrol molecule 104 and a fourthphosphonate molecule 706. As further described herein, the fourthphosphonate molecule 706 depicted in FIG. 7 may be synthesized accordingto one of the processes described herein with respect to FIGS. 8A and8B.

The fourth phosphonate molecule 706 depicted in FIG. 7 represents anexample of a phosphorus-containing molecule in which the additionalreactive group corresponds to an amine group. FIG. 7 illustrates that achloride group of the fourth phosphonate molecule 706 reacts with ahydroxyl group of the resveratrol molecule 104 to form aphosphorus-oxygen single bond between the phosphorus atom of thephosphoryl group and the oxygen atom of the hydroxyl group. As aprophetic example, the resveratrol molecule 104 may be chemicallyreacted with the fourth phosphonate molecule 706 in an amine solvent toyield the fourth resveratrol-based FR small molecule 702.

In the embodiment depicted in FIG. 7, each hydroxyl group of the threehydroxyl groups of the resveratrol molecule 104 chemically reacts withthe chloride group of the fourth phosphonate molecule 706 to form thefourth resveratrol-based FR small molecule 702 having threephosphorus-based flame retardant moieties (and three amine functionalgroups). It will be appreciated that, in other cases, the reactionstoichiometry may be adjusted to form an alternative resveratrol-basedFR small molecule having less than three phosphorus-based flameretardant moieties (and less than three amine functional groups).

Thus, FIG. 7 illustrates an example of a process of forming aresveratrol-based flame retardant small molecule that includes an aminefunctional group via a chemical reaction of a resveratrol molecule and aphosphonate molecule that includes the amine functional group.

FIGS. 8A and 8B are chemical reaction diagrams showing alternativeembodiments of processes of forming the fourth phosphonate molecule 706depicted in FIG. 7. The fourth phosphonate molecule 706 depicted inFIGS. 8A and 8B represents an example of a phosphonate molecule that isfunctionalized with a chloride group for bonding with a hydroxyl groupof a resveratrol molecule and an amine functional group that may beutilized to form a resveratrol-based flame retardant polymer, asdescribed further herein with respect to FIG. 11.

Referring to FIG. 8A, a first chemical reaction diagram 800 illustratesa first embodiment of a process of forming the fourth phosphonatemolecule 706. In FIG. 8A, the fourth phosphonate molecule 706 is formedvia a one-step process via reaction of aminomethanol with phenyldichlorophosphate via careful addition and stoichiometric control.

As a prophetic example, to a stirred solution that includesaminomethanol (1.0 eq.) and triethylamine (2.0 eq.) in anhydrous THF,phenyl dichlorophosphate (1.3 eq.) may be added dropwise at 0° C., andthe reaction mixture may be stirred at ambient temperature for 2 hoursor the reaction mixture may be heated up to reflux (60-65° C.) for anextended reaction time (4 hours). The reaction mixture may be cooled toambient temperature and filtered to remove the triethylaminehydrochloride salt. The solvents of the filtrate may be removed invacuo, and the product may be purified by fractional distillation.

Referring to FIG. 8B, a second chemical reaction diagram 810 illustratesan alternative embodiment of a process of forming the fourth phosphonatemolecule 706. The first chemical reaction depicted in FIG. 8Billustrates that aminomethanol may be reacted with titanium (IV)isopropoxide and phosphonic acid diphenyl ester via apseudo-esterification to form an intermediate molecule. The secondchemical reaction depicted in FIG. 8B illustrates that the intermediatemolecule may be reacted with thionyl chloride to form the fourthphosphonate molecule 706.

As a prophetic example, diaryl phosphite (5.5 mmol) may be added to asolution of titanium (IV) isopropoxide, Ti(OPr)₄ (11 mmol), inaminomethanol (excess). This solution may be diluted with benzene. Thereaction mixture may be heated to 40° C. until completion. The mixturemay be poured into water, extracted with CH₂Cl₂ (3×), dried over MgSO₄,and solvent and volatile components may be removed in vacuo. Theproducts may be purified by fractional distillation orrecrystallization. The product from the first step (1.0 eq.), in dryacetonitrile (MeCN), toluene, or dichloromethane (DCM), may be added toa solution of trichloroisocyanuric acid (0.33 eq.), N-chlorosuccinimide(1.0 eq.), or tert-butyl hypochlorite (1.0 eq.) in the same solvent atroom temperature, under an N₂ atmosphere. Upon formation of aprecipitate, the reaction may be stirred at room temperature for anadditional 2 hours. Upon completion of the reaction, as determined by³¹P NMR, the reaction mixture may be passed through a 0.45 μm Whatmansyringe filter and concentrated under vacuum. Next, thionyl chloride(SOCl₂) may be dissolved in a suitable solvent, such as carbontetrachloride (CCl₄), and the chemical reaction may be performed from 0°C. to room temperature.

Thus, FIGS. 8A and 8B illustrate alternative processes of forming aphosphonate molecule that is functionalized with a chloride group forbonding with a hydroxyl group of a resveratrol molecule and an aminefunctional group that may be utilized to form a resveratrol-based flameretardant polymer. While FIGS. 8A and 8B illustrate an example in whichthe phosphonate molecule includes a phenyl group, it will be appreciatedthat the phenyl group may be substituted by ethyl, methyl, propyl, orisopropyl groups, among other alternatives.

Referring to FIG. 9, a chemical reaction diagram 900 illustrates aprocess of forming a fifth resveratrol-based FR small molecule 902,according to one embodiment. In the particular embodiment depicted inFIG. 9, the fifth resveratrol-based FR small molecule 902 is formed viaa chemical reaction of the resveratrol molecule 104 and a fifthphosphonate molecule 906. As further described herein, the fifthphosphonate molecule 906 depicted in FIG. 9 may be synthesized accordingto one of the processes described herein with respect to FIGS. 10A and10B.

The fifth phosphonate molecule 906 depicted in FIG. 9 represents anexample of a phosphorus-containing molecule in which the additionalreactive group corresponds to a carboxyl group. FIG. 9 illustrates thata chloride group of the fifth phosphonate molecule 906 reacts with ahydroxyl group of the resveratrol molecule 104 to form aphosphorus-oxygen single bond between the phosphorus atom of thephosphoryl group and the oxygen atom of the hydroxyl group. As aprophetic example, the resveratrol molecule 104 may be chemicallyreacted with the fifth phosphonate molecule 906 in an amine solvent toyield the fifth resveratrol-based FR small molecule 902.

In the embodiment depicted in FIG. 9, each hydroxyl group of the threehydroxyl groups of the resveratrol molecule 104 chemically reacts withthe chloride group of the fifth phosphonate molecule 906 to form thefifth resveratrol-based FR small molecule 902 having threephosphorus-based flame retardant moieties (and three carboxyl functionalgroups). It will be appreciated that, in other cases, the reactionstoichiometry may be adjusted to form an alternative resveratrol-basedFR small molecule having less than three phosphorus-based flameretardant moieties (and less than three carboxyl functional groups).

Thus, FIG. 9 illustrates an example of a process of forming aresveratrol-based flame retardant small molecule that includes acarboxyl functional group via a chemical reaction of a resveratrolmolecule and a phosphonate molecule that includes the carboxylfunctional group.

FIGS. 10A and 10B are chemical reaction diagrams showing alternativeembodiments of processes of forming the fifth phosphonate molecule 906depicted in FIG. 9. The fifth phosphonate molecule 906 depicted in FIGS.10A and 10B represents an example of a phosphonate molecule that isfunctionalized with a chloride group for bonding with a hydroxyl groupof a resveratrol molecule and a carboxyl functional group that may beutilized to form a resveratrol-based flame retardant polymer, asdescribed further herein with respect to FIG. 11.

Referring to FIG. 10A, a first chemical reaction diagram 1000illustrates a first embodiment of a process of forming the fifthphosphonate molecule 906. In FIG. 10A, the fifth phosphonate molecule906 is formed via a one-step process via reaction of an α-hydroxy acid(e.g., glycolic acid) with phenyl dichlorophosphate via careful additionand stoichiometric control.

As a prophetic example, to a stirred solution that includes glycolicacid (1.0 eq.) and triethylamine (2.0 eq.) in anhydrous THF, phenyldichlorophosphate (1.3 eq.) may be added dropwise at 0° C., and thereaction mixture may be stirred at ambient temperature for 2 hours orthe reaction mixture may be heated up to reflux (60-65° C.) for anextended reaction time (4 hours). The reaction mixture may be cooled toambient temperature and filtered to remove the triethylaminehydrochloride salt. The solvents of the filtrate may be removed invacuo, and the product may be purified by fractional distillation.

Referring to FIG. 10B, a second chemical reaction diagram 1010illustrates an alternative embodiment of a process of forming the fifthphosphonate molecule 906. The first chemical reaction depicted in FIG.10B illustrates that an α-hydroxy acid (e.g., glycolic acid) may bereacted with titanium (IV) isopropoxide and phosphonic acid diphenylester via a pseudo-esterification to form an intermediate molecule. Thesecond chemical reaction depicted in FIG. 10B illustrates that theintermediate molecule may be reacted with thionyl chloride to form thefifth phosphorus-based FR molecule.

As a prophetic example, diaryl phosphite (5.5 mmol) may be added to asolution of titanium (IV) isopropoxide, Ti(OPr)₄ (11 mmol), in glycolicacid (excess). This solution may be diluted with benzene. The reactionmixture may be heated to 40° C. until completion. The mixture may bepoured into water, extracted with CH₂Cl₂ (3×), dried over MgSO₄, andsolvent and volatile components may be removed in vacuo. The productsmay be purified by fractional distillation or recrystallization. Theproduct from the first step (1.0 eq.), in dry acetonitrile (MeCN),toluene, or dichloromethane (DCM), may be added to a solution oftrichloroisocyanuric acid (0.33 eq.), N-chlorosuccinimide (1.0 eq.), ortert-butyl hypochlorite (1.0 eq.) in the same solvent at roomtemperature, under an N₂ atmosphere. Upon formation of a precipitate,the reaction may be stirred at room temperature for an additional 2hours. Upon completion of the reaction, as determined by ³¹P NMR, thereaction mixture may be passed through a 0.45 μm Whatman syringe filterand concentrated under vacuum. Next, thionyl chloride (SOCl₂) may bedissolved in a suitable solvent, such as carbon tetrachloride (CCl₄),and the chemical reaction may be performed from 0° C. to roomtemperature.

Thus, FIGS. 10A and 10B illustrate alternative processes of forming aphosphonate molecule that is functionalized with a chloride group forbonding with a hydroxyl group of a resveratrol molecule and a carboxylfunctional group that may be utilized to form a resveratrol-derivedflame retardant polymer. While FIGS. 10A and 10B illustrate an examplein which the phosphonate molecule includes a phenyl group, it will beappreciated that the phenyl group may be substituted by ethyl, methyl,propyl, or isopropyl groups, among other alternatives.

Referring to FIG. 11, a diagram 1100 illustrates a first example of aresveratrol-based flame retardant polymer 1102 that may be formed fromone of the resveratrol-based flame retardant small molecules depicted inFIGS. 1, 3, 5, 7, and 9.

Referring to FIG. 12, a chemical reaction diagram 1200 illustrates aprocess of forming a sixth resveratrol-based FR small molecule 1202,according to one embodiment. In the particular embodiment depicted inFIG. 12, the sixth resveratrol-based FR small molecule 1202 is formedvia a chemical reaction of the resveratrol molecule 104 and a firstphosphinate molecule 1206. As further described herein, the firstphosphinate molecule 1206 depicted in FIG. 12 may be synthesizedaccording to one of the processes described herein with respect to FIGS.13A and 13B.

The first phosphinate molecule 1206 depicted in FIG. 12 represents anexample of a phosphorus-containing molecule in which the additionalreactive group corresponds to an allyl group. FIG. 12 illustrates that achloride group of the first phosphinate molecule 1206 reacts with ahydroxyl group of the resveratrol molecule 104 to form aphosphorus-oxygen single bond between the phosphorus atom of thephosphoryl group and the oxygen atom of the hydroxyl group. As aprophetic example, the resveratrol molecule 104 may be chemicallyreacted with the first phosphinate molecule 1206 in an amine solvent toyield the sixth resveratrol-based FR small molecule 1202.

In the embodiment depicted in FIG. 12, each hydroxyl group of the threehydroxyl groups of the resveratrol molecule 104 chemically reacts withthe chloride group of the first phosphinate molecule 1206 to form thesixth resveratrol-based FR small molecule 1202 having threephosphorus-based flame retardant moieties (and three allyl functionalgroups). It will be appreciated that, in other cases, the reactionstoichiometry may be adjusted to form an alternative resveratrol-basedFR small molecule having less than three phosphorus-based flameretardant moieties (and less than three allyl functional groups).

Thus, FIG. 12 illustrates an example of a process of forming aresveratrol-based flame retardant small molecule that includes an allylfunctional group via a chemical reaction of a resveratrol molecule and aphosphinate molecule that includes the allyl functional group.

FIGS. 13A and 13B are chemical reaction diagrams showing alternativeembodiments of processes of forming the first phosphinate molecule 1206depicted in FIG. 12. The first phosphinate molecule 1206 depicted inFIGS. 13A and 13B represents an example of a phosphinate molecule thatis functionalized with a chloride group for bonding with a hydroxylgroup of a resveratrol molecule and an allyl functional group that maybe utilized to form a resveratrol-based flame retardant polymer, asdescribed further herein with respect to FIG. 22.

Referring to FIG. 13A, a first chemical reaction diagram 1300illustrates a first embodiment of a process of forming the firstphosphinate molecule 1206. In the first chemical reaction depicted inFIG. 13A, an allyl chloride molecule is chemically reacted withtriphenylphosphite to form a phosphonyl ester intermediate material. Inthe second chemical reaction depicted in FIG. 13A, the phosphonyl esterintermediate material is chemically reacted with phosphoruspentachloride to form the first phosphinate molecule 1206.

As a prophetic example, allyl chloride (1 eq.) and trialkyl phosphite,P(OR)₃, may be added to a reaction vessel. The reaction vessel mayinclude an organic solvent such as toluene, THF, ethanol, or DMF, andmay also contain a compound such an alumina. The reaction may be heatedto reflux or up to 180° C. if done using neat conditions. The reactionmixture may also be irradiated by microwaves for a short period toincrease the reaction rate. The reaction may be cooled to roomtemperature, and the excess trialkyl phosphite may be removed in vacuoor it may be washed with DCM, and dried using CaCl₂ prior to filtrationand having the solvents removed in vacuo. The phosphonate may bepurified by fractional distillation. To a solution of the phosphonateproduct may be added PCl₅ (excess) at 0° C. under an inert atmosphere.The reaction may be performed in a solvent such as CCl₄. The mixture maybe allowed to warm up to room temperature and may be stirred for anadditional day. The solvent may then be removed in vacuo, and theresidue may be distilled to give the product.

Referring to FIG. 13B, a second chemical reaction diagram 1310illustrates an alternative embodiment of a process of forming the firstphosphinate molecule 1206. In the first chemical reaction depicted inFIG. 13B, an allyl chloride molecule is chemically reacted withtriphenylphosphite and quenched under aqueous basic conditions to form aphosphonyl ester intermediate material. In the second chemical reactiondepicted in FIG. 13B, the phosphonyl ester intermediate material ischemically reacted with thionyl chloride to form the first phosphinatemolecule 1206.

As a prophetic example, an allyl phosphonate (1.0 eq.) may be generatedand quickly added to a solution of bromodimethyl borane (1.0 eq.) in anorganic solvent such as toluene. The reaction mixture may be warmed toroom temperature and stirred overnight. The solvent and volatilebyproducts may be removed in vacuo. To a solution of the diarylphosphorous-containing product, SOCl₂ (excess) may be added at 0° C. Themixture may be allowed to warm up to room temperature or heated to 40°C. and may be stirred for an additional day. The solvent may then beremoved in vacuo, and the residue may be distilled to give the product.

Thus, FIGS. 13A and 13B illustrate alternative processes of forming aphosphinate molecule that is functionalized with a chloride group forbonding with a hydroxyl group of a resveratrol molecule and an allylfunctional group that may be utilized to form a resveratrol-based flameretardant polymer. While FIGS. 13A and 13B illustrate an example inwhich the phosphinate molecule includes a phenyl group, it will beappreciated that the phenyl group may be substituted by ethyl, methyl,propyl, or isopropyl groups, among other alternatives.

Referring to FIG. 14, a chemical reaction diagram 1400 illustrates aprocess of forming a seventh resveratrol-based FR small molecule 1402,according to one embodiment. In the particular embodiment depicted inFIG. 14, the seventh resveratrol-based FR small molecule 1402 is formedvia a chemical reaction of the resveratrol molecule 104 and a secondphosphinate molecule 1406. As further described herein, the secondphosphinate molecule 1406 depicted in FIG. 14 may be synthesizedaccording to one of the processes described herein with respect to FIGS.15A and 15B.

The second phosphinate molecule 1406 depicted in FIG. 14 represents anexample of a phosphorus-containing molecule in which the additionalreactive group corresponds to an epoxide group. FIG. 14 illustrates thata chloride group of the second phosphinate molecule 1406 reacts with ahydroxyl group of the resveratrol molecule 104 to form aphosphorus-oxygen single bond between the phosphorus atom of thephosphoryl group and the oxygen atom of the hydroxyl group. As aprophetic example, the resveratrol molecule 104 may be chemicallyreacted with the second phosphinate molecule 1406 in an amine solvent toyield the seventh resveratrol-based FR small molecule 1402.

In the embodiment depicted in FIG. 14, each hydroxyl group of the threehydroxyl groups of the resveratrol molecule 104 chemically reacts withthe chloride group of the second phosphinate molecule 1406 to form theseventh resveratrol-based FR small molecule 1402 having threephosphorus-based flame retardant moieties (and three epoxide functionalgroups). It will be appreciated that, in other cases, the reactionstoichiometry may be adjusted to form an alternative resveratrol-basedFR small molecule having less than three phosphorus-based flameretardant moieties (and less than three epoxide functional groups).

Thus, FIG. 14 illustrates an example of a process of forming aresveratrol-derived flame retardant small molecule that includes anepoxide functional group via a chemical reaction of a resveratrolmolecule and a phosphinate molecule that includes the epoxide functionalgroup.

FIGS. 15A and 15B are chemical reaction diagrams showing alternativeembodiments of processes of forming the second phosphinate molecule 1406depicted in FIG. 14. The second phosphinate molecule 1406 depicted inFIGS. 15A and 15B represents an example of a phosphinate molecule thatis functionalized with a chloride group for bonding with a hydroxylgroup of a resveratrol molecule and an epoxide functional group that maybe utilized to form a resveratrol-based flame retardant polymer, asdescribed further herein with respect to FIG. 22.

Referring to FIG. 15A, a first chemical reaction diagram 1500illustrates a first embodiment of a process of forming the secondphosphinate molecule 1406. In the first chemical reaction depicted inFIG. 15A, an epichlorohydrin molecule is chemically reacted withtriphenylphosphite to form a phosphonyl ester intermediate material. Inthe second chemical reaction depicted in FIG. 15A, the phosphonyl esterintermediate material is chemically reacted with phosphoruspentachloride to form the second phosphinate molecule 1406.

As a prophetic example, epichlorohydrin (1 eq.) and trialkyl phosphite,P(OR)₃, may be added to a reaction vessel. The reaction vessel mayinclude an organic solvent such as toluene, THF, ethanol, or DMF, andmay also contain a compound such an alumina. The reaction may be heatedto reflux or up to 180° C. if done using neat conditions. The reactionmixture may also be irradiated by microwaves for a short period toincrease the reaction rate. The reaction may be cooled to roomtemperature, and the excess trialkyl phosphite may be removed in vacuoor it may be washed with DCM, and dried using CaCl₂ prior to filtrationand having the solvents removed in vacuo. The phosphonate may bepurified by fractional distillation. To a solution of the phosphonateproduct may be added PCl₅ (excess) at 0° C. under an inert atmosphere.The reaction may be performed in a solvent such as CCl₄. The mixture maybe allowed to warm up to room temperature and may be stirred for anadditional day. The solvent may then be removed in vacuo, and theresidue may be distilled to give the product.

Referring to FIG. 15B, a second chemical reaction diagram 1510illustrates an alternative embodiment of a process of forming the secondphosphinate molecule 1406. In the first chemical reaction depicted inFIG. 15B, an epichlorohydrin molecule is chemically reacted withtriphenylphosphite and quenched under aqueous basic conditions to form aphosphonyl ester intermediate material. In the second chemical reactiondepicted in FIG. 15B, the phosphonyl ester intermediate material ischemically reacted with thionyl chloride to form the second phosphinatemolecule 1406.

As a prophetic example, an oxirane phosphonate (1.0 eq.) may begenerated and quickly added to a solution of bromodimethyl borane (1.0eq.) in an organic solvent such as toluene. The reaction mixture may bewarmed to room temperature and stirred overnight. The solvent andvolatile byproducts may be removed in vacuo. To a solution of the diarylphosphorous-containing product, SOCl₂ (excess) may be added at 0° C. Themixture may be allowed to warm up to room temperature or heated to 40°C. and may be stirred for an additional day. The solvent may then beremoved in vacuo, and the residue may be distilled to give the product.

Thus, FIGS. 15A and 15B illustrate alternative processes of forming aphosphinate molecule that is functionalized with a chloride group forbonding with a hydroxyl group of a resveratrol molecule and an epoxidefunctional group that may be utilized to form a resveratrol-based flameretardant polymer. While FIGS. 15A and 15B illustrate an example inwhich the phosphinate molecule includes a phenyl group, it will beappreciated that the phenyl group may be substituted by ethyl, methyl,propyl, or isopropyl groups, among other alternatives.

Referring to FIG. 16, a chemical reaction diagram 1600 illustrates aprocess of forming an eighth resveratrol-based FR small molecule 1602,according to one embodiment. In the particular embodiment depicted inFIG. 16, the eighth resveratrol-based FR small molecule 1602 is formedvia a chemical reaction of the resveratrol molecule 104 and a thirdphosphinate molecule 1606. As further described herein, the thirdphosphinate molecule 1606 depicted in FIG. 16 may be synthesizedaccording to one of the processes described herein with respect to FIGS.17A and 17B.

The third phosphinate molecule 1606 depicted in FIG. 16 represents anexample of a phosphorus-containing molecule in which the additionalreactive group corresponds to a lactone group. FIG. 16 illustrates thata chloride group of the third phosphinate molecule 1606 reacts with ahydroxyl group of the resveratrol molecule 104 to form aphosphorus-oxygen single bond between the phosphorus atom of thephosphoryl group and the oxygen atom of the hydroxyl group. As aprophetic example, the resveratrol molecule 104 may be chemicallyreacted with the third phosphinate molecule 1606 in an amine solvent toyield the eighth resveratrol-based FR small molecule 1602.

In the embodiment depicted in FIG. 16, each hydroxyl group of the threehydroxyl groups of the resveratrol molecule 104 chemically reacts withthe chloride group of the third phosphinate molecule 1606 to form theeighth resveratrol-based FR small molecule 1602 having threephosphorus-based flame retardant moieties (and three lactone functionalgroups). It will be appreciated that, in other cases, the reactionstoichiometry may be adjusted to form an alternative resveratrol-basedFR small molecule having less than three phosphorus-based flameretardant moieties (and less than three lactone functional groups).

Thus, FIG. 16 illustrates an example of a process of forming aresveratrol-based flame retardant small molecule that includes a lactonefunctional group via a chemical reaction of a resveratrol molecule and aphosphinate molecule that includes the lactone functional group.

FIGS. 17A and 17B are chemical reaction diagrams showing alternativeembodiments of processes of forming the third phosphinate molecule 1606depicted in FIG. 16. The third phosphinate molecule 1606 depicted inFIGS. 17A and 17B represents an example of a phosphinate molecule thatis functionalized with a chloride group for bonding with a hydroxylgroup of a resveratrol molecule and a lactone functional group that maybe utilized to form a resveratrol-based flame retardant polymer, asdescribed further herein with respect to FIG. 22.

Referring to FIG. 17A, a first chemical reaction diagram 1700illustrates a first embodiment of a process of forming the thirdphosphinate molecule 1606. In the first chemical reaction depicted inFIG. 17A, a (chloromethyl)ethylene carbonate molecule is chemicallyreacted with triphenylphosphite to form a phosphonyl ester intermediatematerial. In the second chemical reaction depicted in FIG. 17A, thephosphonyl ester intermediate material is chemically reacted withphosphorus pentachloride to form the third phosphinate molecule 1606.

As a prophetic example, (chloromethyl)ethylene carbonate (1 eq.) andtrialkyl phosphite, P(OR)₃, may be added to a reaction vessel. Thereaction vessel may include an organic solvent such as toluene, THF,ethanol, or DMF, and may also contain a compound such an alumina. Thereaction may be heated to reflux or up to 180° C. if done using neatconditions. The reaction mixture may also be irradiated by microwavesfor a short period to increase the reaction rate. The reaction may becooled to room temperature, and the excess trialkyl phosphite may beremoved in vacuo or it may be washed with DCM, and dried using CaCl₂prior to filtration and having the solvents removed in vacuo. Thephosphonate may be purified by fractional distillation. To a solution ofthe phosphonate product may be added PCl₅ (excess) at 0° C. under aninert atmosphere. The reaction may be performed in a solvent such asCCl₄. The mixture may be allowed to warm up to room temperature and maybe stirred for an additional day. The solvent may then be removed invacuo, and the residue may be distilled to give the product.

Referring to FIG. 17B, a second chemical reaction diagram 1710illustrates an alternative embodiment of a process of forming the thirdphosphinate molecule 1606. In the first chemical reaction depicted inFIG. 17B, a (chloromethyl)ethylene carbonate molecule is chemicallyreacted with triphenylphosphite and quenched under aqueous basicconditions to form a phosphonyl ester intermediate material. In thesecond chemical reaction depicted in FIG. 17B, the phosphonyl esterintermediate material is chemically reacted with thionyl chloride toform the third phosphinate molecule 1606.

As a prophetic example, a lactone phosphonate (1.0 eq.) may be generatedand quickly added to a solution of bromodimethyl borane (1.0 eq.) in anorganic solvent such as toluene. The reaction mixture may be warmed toroom temperature and stirred overnight. The solvent and volatilebyproducts may be removed in vacuo. To a solution of the diarylphosphorous-containing product, SOCl₂ (excess) may be added at 0° C. Themixture may be allowed to warm up to room temperature or heated to 40°C. and may be stirred for an additional day. The solvent may then beremoved in vacuo, and the residue may be distilled to give the product.

Thus, FIGS. 17A and 17B illustrate alternative processes of forming aphosphinate molecule that is functionalized with a chloride group forbonding with a hydroxyl group of a resveratrol molecule and a lactonefunctional group that may be utilized to form a resveratrol-based flameretardant polymer. While FIGS. 17A and 17B illustrate an example inwhich the phosphinate molecule includes a phenyl group, it will beappreciated that the phenyl group may be substituted by ethyl, methyl,propyl, or isopropyl groups, among other alternatives.

Referring to FIG. 18, a chemical reaction diagram 1800 illustrates aprocess of forming a ninth resveratrol-based FR small molecule 1802,according to one embodiment. In the particular embodiment depicted inFIG. 18, the ninth resveratrol-based FR small molecule 1802 is formedvia a chemical reaction of the resveratrol molecule 104 and a fourthphosphinate molecule 1806. As further described herein, the fourthphosphinate molecule 1806 depicted in FIG. 18 may be synthesizedaccording to one of the processes described herein with respect to FIGS.19A and 19B.

The fourth phosphinate molecule 1806 depicted in FIG. 18 represents anexample of a phosphorus-containing molecule in which the additionalreactive group corresponds to an amine group. FIG. 18 illustrates that achloride group of the fourth phosphinate molecule 1806 reacts with ahydroxyl group of the resveratrol molecule 104 to form aphosphorus-oxygen single bond between the phosphorus atom of thephosphoryl group and the oxygen atom of the hydroxyl group. As aprophetic example, the resveratrol molecule 104 may be chemicallyreacted with the fourth phosphinate molecule 1806 in an amine solvent toyield the ninth resveratrol-based FR small molecule 1802.

In the embodiment depicted in FIG. 18, each hydroxyl group of the threehydroxyl groups of the resveratrol molecule 104 chemically reacts withthe chloride group of the fourth phosphinate molecule 1806 to form theninth resveratrol-based FR small molecule 1802 having threephosphorus-based flame retardant moieties (and three amine functionalgroups). It will be appreciated that, in other cases, the reactionstoichiometry may be adjusted to form an alternative resveratrol-basedFR small molecule having less than three phosphorus-based flameretardant moieties (and less than three amine functional groups).

Thus, FIG. 18 illustrates an example of a process of forming aresveratrol-based flame retardant small molecule that includes an aminefunctional group via a chemical reaction of a resveratrol molecule and aphosphinate molecule that includes the amine functional group.

FIGS. 19A and 19B are chemical reaction diagrams showing alternativeembodiments of processes of forming the fourth phosphinate molecule 1806depicted in FIG. 18. The fourth phosphinate molecule 1806 depicted inFIGS. 19A and 19B represents an example of a phosphinate molecule thatis functionalized with a chloride group for bonding with a hydroxylgroup of a resveratrol molecule and an amine functional group that maybe utilized to form a resveratrol-based flame retardant polymer, asdescribed further herein with respect to FIG. 22.

Referring to FIG. 19A, a first chemical reaction diagram 1900illustrates a first embodiment of a process of forming the fourthphosphinate molecule 1806. In the first chemical reaction depicted inFIG. 19A, a chloromethylamine molecule is chemically reacted withtriphenylphosphite to form a phosphonyl ester intermediate material. Inthe second chemical reaction depicted in FIG. 19A, the phosphonyl esterintermediate material is chemically reacted with phosphoruspentachloride to form the fourth phosphinate molecule 1806.

As a prophetic example, chloromethylamine (1 eq.) and trialkylphosphite, P(OR)₃, may be added to a reaction vessel. The reactionvessel may include an organic solvent such as toluene, THF, ethanol, orDMF, and may also contain a compound such an alumina. The reaction maybe heated to reflux or up to 180° C. if done using neat conditions. Thereaction mixture may also be irradiated by microwaves for a short periodto increase the reaction rate. The reaction may be cooled to roomtemperature, and the excess trialkyl phosphite may be removed in vacuoor it may be washed with DCM, and dried using CaCl₂ prior to filtrationand having the solvents removed in vacuo. The phosphonate may bepurified by fractional distillation. To a solution of the phosphonateproduct may be added PCl₅ (excess) at 0° C. under an inert atmosphere.The reaction may be performed in a solvent such as CCl₄. The mixture maybe allowed to warm up to room temperature and may be stirred for anadditional day. The solvent may then be removed in vacuo, and theresidue may be distilled to give the product.

Referring to FIG. 19B, a second chemical reaction diagram 1910illustrates an alternative embodiment of a process of forming the fourthphosphinate molecule 1806. In the first chemical reaction depicted inFIG. 19B, a chloromethylamine molecule is chemically reacted withtriphenylphosphite and quenched under aqueous basic conditions to form aphosphonyl ester intermediate material. In the second chemical reactiondepicted in FIG. 19B, the phosphonyl ester intermediate material ischemically reacted with thionyl chloride to form the fourth phosphinatemolecule 1806.

As a prophetic example, an amine phosphonate (1.0 eq.) may be generatedand quickly added to a solution of bromodimethyl borane (1.0 eq.) in anorganic solvent such as toluene. The reaction mixture may be warmed toroom temperature and stirred overnight. The solvent and volatilebyproducts may be removed in vacuo. To a solution of the diarylphosphorous-containing product, SOCl₂ (excess) may be added at 0° C. Themixture may be allowed to warm up to room temperature or heated to 40°C. and may be stirred for an additional day. The solvent may then beremoved in vacuo, and the residue may be distilled to give the product.

Thus, FIGS. 19A and 19B illustrate alternative processes of forming aphosphinate molecule that is functionalized with a chloride group forbonding with a hydroxyl group of a resveratrol molecule and an aminefunctional group that may be utilized to form a resveratrol-derivedflame retardant polymer. While FIGS. 19A and 19B illustrate an examplein which the phosphinate molecule includes a phenyl group, it will beappreciated that the phenyl group may be substituted by ethyl, methyl,propyl, or isopropyl groups, among other alternatives.

Referring to FIG. 20, a chemical reaction diagram 2000 illustrates aprocess of forming a tenth resveratrol-based FR small molecule 2002,according to one embodiment. In the particular embodiment depicted inFIG. 20, the tenth resveratrol-based FR small molecule 2002 is formedvia a chemical reaction of the resveratrol molecule 104 and a fifthphosphinate molecule 2006. As further described herein, the fifthphosphinate molecule 2006 depicted in FIG. 20 may be synthesizedaccording to one of the processes described herein with respect to FIGS.21A and 21B.

The fifth phosphinate molecule 2006 depicted in FIG. 20 represents anexample of a phosphorus-containing molecule in which the additionalreactive group corresponds to a carboxyl group. FIG. 20 illustrates thata chloride group of the fifth phosphinate molecule 2006 reacts with ahydroxyl group of the resveratrol molecule 104 to form aphosphorus-oxygen single bond between the phosphorus atom of thephosphoryl group and the oxygen atom of the hydroxyl group. As aprophetic example, the resveratrol molecule 104 may be chemicallyreacted with the fifth phosphinate molecule 2006 in an amine solvent toyield the tenth resveratrol-based FR small molecule 2002.

In the embodiment depicted in FIG. 20, each hydroxyl group of the threehydroxyl groups of the resveratrol molecule 104 chemically reacts withthe chloride group of the fifth phosphinate molecule 2006 to form thetenth resveratrol-based FR small molecule 2002 having threephosphorus-based flame retardant moieties (and three carboxyl functionalgroups). It will be appreciated that, in other cases, the reactionstoichiometry may be adjusted to form an alternative resveratrol-basedFR small molecule having less than three phosphorus-based flameretardant moieties (and less than three carboxyl functional groups).

Thus, FIG. 20 illustrates an example of a process of forming aresveratrol-based flame retardant small molecule that includes acarboxyl functional group via a chemical reaction of a resveratrolmolecule and a phosphinate molecule that includes the carboxylfunctional group.

FIGS. 21A and 21B are chemical reaction diagrams showing alternativeembodiments of processes of forming the fifth phosphinate molecule 2006depicted in FIG. 20. The fifth phosphinate molecule 2006 depicted inFIGS. 21A and 21B represents an example of a phosphinate molecule thatis functionalized with a chloride group for bonding with a hydroxylgroup of a resveratrol molecule and a carboxyl functional group that maybe utilized to form a resveratrol-based flame retardant polymer, asdescribed further herein with respect to FIG. 22.

Referring to FIG. 21A, a first chemical reaction diagram 2100illustrates a first embodiment of a process of forming the fifthphosphinate molecule 2006. In the first chemical reaction depicted inFIG. 21A, a chloroacetic acid molecule is chemically reacted withtriphenylphosphite to form a phosphonyl ester intermediate material. Inthe second chemical reaction depicted in FIG. 21A, the phosphonyl esterintermediate material is chemically reacted with phosphoruspentachloride to form the fifth phosphinate molecule 2006.

As a prophetic example, chloroacetic acid (1 eq.) and trialkylphosphite, P(OR)₃, may be added to a reaction vessel. The reactionvessel may include an organic solvent such as toluene, THF, ethanol, orDMF, and may also contain a compound such an alumina. The reaction maybe heated to reflux or up to 180° C. if done using neat conditions. Thereaction mixture may also be irradiated by microwaves for a short periodto increase the reaction rate. The reaction may be cooled to roomtemperature, and the excess trialkyl phosphite may be removed in vacuoor it may be washed with DCM, and dried using CaCl₂ prior to filtrationand having the solvents removed in vacuo. The phosphonate may bepurified by fractional distillation. To a solution of the phosphonateproduct may be added PCl₅ (excess) at 0° C. under an inert atmosphere.The reaction may be performed in a solvent such as CCl₄. The mixture maybe allowed to warm up to room temperature and may be stirred for anadditional day. The solvent may then be removed in vacuo, and theresidue may be distilled to give the product.

Referring to FIG. 21B, a second chemical reaction diagram 2110illustrates an alternative embodiment of a process of forming the fifthphosphinate molecule 2006. In the first chemical reaction depicted inFIG. 21B, a chloroacetic acid molecule is chemically reacted withtriphenylphosphite and quenched under aqueous basic conditions to form aphosphonyl ester intermediate material. In the second chemical reactiondepicted in FIG. 21B, the phosphonyl ester intermediate material ischemically reacted with thionyl chloride to form the fifth phosphinatemolecule 2006.

As a prophetic example, a carboxyl phosphonate (1.0 eq.) may begenerated and quickly added to a solution of bromodimethyl borane (1.0eq.) in an organic solvent such as toluene. The reaction mixture may bewarmed to room temperature and stirred overnight. The solvent andvolatile byproducts may be removed in vacuo. To a solution of the diarylphosphorous-containing product, SOCl₂ (excess) may be added at 0° C. Themixture may be allowed to warm up to room temperature or heated to 40°C. and may be stirred for an additional day. The solvent may then beremoved in vacuo, and the residue may be distilled to give the product.

Thus, FIGS. 21A and 21B illustrate alternative processes of forming aphosphinate molecule that is functionalized with a chloride group forbonding with a hydroxyl group of a resveratrol molecule and a carboxylfunctional group that may be utilized to form a resveratrol-based flameretardant polymer. While FIGS. 21A and 21B illustrate an example inwhich the phosphinate molecule includes a phenyl group, it will beappreciated that the phenyl group may be substituted by ethyl, methyl,propyl, or isopropyl groups, among other alternatives.

Referring to FIG. 22, a diagram 2200 illustrates a second example of aresveratrol-based flame retardant polymer 2202 that may be formed fromone of the resveratrol-based flame retardant small molecules depicted inFIGS. 12, 14, 16, 18, and 20.

It will be understood from the foregoing description that modificationsand changes may be made in various embodiments of the present inventionwithout departing from its true spirit. The descriptions in thisspecification are for purposes of illustration only and are not to beconstrued in a limiting sense. The scope of the present invention islimited only by the language of the following claims.

1.-20. (canceled)
 21. A resveratrol-based flame retardant compoundhaving the following structural formula:

wherein X includes a terminal functional group selected from the groupconsisting of: an allyl group; an epoxide group; an ethylene carbonategroup; an amine group; and a carboxyl group.
 22. The resveratrol-basedflame retardant compound of claim 21, having the following structuralformula:


23. The resveratrol-based flame retardant compound of claim 21, havingthe following structural formula:


24. The resveratrol-based flame retardant compound of claim 21, havingthe following structural formula:


25. The resveratrol-based flame retardant compound of claim 21, havingthe following structural formula:


26. The resveratrol-based flame retardant compound of claim 21, havingthe following structural formula:


27. A resveratrol-based flame retardant compound having the followingstructural formula:

wherein R corresponds to an alkyl group; and wherein X includes aterminal functional group selected from the group consisting of: anallyl group; an epoxide group; an ethylene carbonate group; an aminegroup; and a carboxyl group.
 28. The resveratrol-based flame retardantcompound of claim 27, having the following structural formula:


29. The resveratrol-based flame retardant compound of claim 27, havingthe following structural formula:


30. The resveratrol-based flame retardant compound of claim 27, havingthe following structural formula:


31. The resveratrol-based flame retardant compound of claim 27, havingthe following structural formula:


32. The resveratrol-based flame retardant compound of claim 27, havingthe following structural formula: